Rheology stabilizer for cementitious compositions

ABSTRACT

An admixture formulation of at least one polycarboxylate dispersant and at least one naphthalene dispersant is provided. When the polycarboxylate dispersant and the naphthalene dispersant of the admixture formulation are combined at various ratios the admixture formulation reduces the tendency for bleed and segregation in cementitious mixtures without increasing water demand, retarding setting, increasing water sensitivity, promoting high viscosity, or reducing flow retention.

BACKGROUND

[0001] In recent years concrete and mortar systems have beenincreasingly used in flowable, fluid, or self-consolidatingconsistencies in an attempt to increase the speed of construction. Onemethod that is used to facilitate placement of these high slump mixturesis pumping. Pumped cementitious compositions such as concrete, mortar orgrouts are conveyed by pressure through either rigid pipes or flexiblehoses and discharged directly into the required area. Pumping may beused for most concrete construction, but it is especially useful wherespace or access for construction equipment is limited.

[0002] Under pressure and motion, a small amount of water is transmittedfrom the cementitious composition to the sidewall of the pipe in orderto provide a lubricating layer. The only element of a cementitiouscomposition that is pumpable is water, and it is the stability of thewater in the mix under pressure that largely determines pumpability.When a cementitious composition blocks a pipeline there is a process ofwater loss, that is, a process in which the prevailing axial pressure inthe pipe forces the water to move faster than the cementitiouscomposition, leaving a portion of it drier than needed for the saturatedstate. Addition of cement and fine aggregates having grain sizes of lessthan 300 μm inhibits the migration of water under pumping pressure.Sometimes high contents of cement and fine aggregates increase the flowresistance, the reason being that such mixtures have too muchcohesiveness, which produces a high viscosity that prevents thedevelopment of an adequate lubricating layer.

[0003] After placement of the cementitious composition, the mixture mustalso remain homogeneous. Settlement of the denser portions of themixture can involve separation of water (bleeding) as well asstratification of the coarse fractions due to density differences(segregation). Bleeding causes a high water to binder ratio at the topsurface of the cementitious composition, as well as deposition of anexcess proportion of fine material in the upper region of thecementitious composition. This causes lower strength, higher shrinkage,and in applications where the upper surface must support load (such asgrouting), the inability of the material to function as intended.Likewise, segregation of the aggregate portion of the cementitiouscomposition produces an inhomogeneous composition with differingproperties throughout the installed cementitious composition.

[0004] The increase in slump of mortar and concrete mixes can alsoincrease the tendency to lose water as well as allow the settlement ofthe coarse particles of the mixture (segregation).This water separationfrom the mixture is known as “bleeding”. Both bleeding and segregationcan happen under the influence of gravity, as well as be increasedthrough the use of additives commonly used to improve fluidity.

[0005] Admixtures may help the process of pumping, such aswater-reducing admixtures like sulfonated naphthalene-formaldehydecondensate (SNF) which reduce the flow resistance when used withunchanged water contents, to obtain more fluid consistencies.Water-reducing admixtures improve the dispersion of the cement grainsand minimize the agglomeration tendency.

[0006] A number of water-soluble polymers have long been used asthickening or stabilizing additives to minimize segregation and bleedingissues of cementing compositions. Such polymers could be alkylderivatives of cellulose, for example methylcellulose, hydroxymethyl,hydroxyethyl, or hydroxypropyl cellulose, and the like, clays, guar gum,welan gum or other esterified polysaccharides. These water solublepolymers serve as a “suspending aid” by reducing the tendency ofaggregates in fresh cementitious compositions to settle, and of mixingwater to bleed on the surface. They provide an improved cohesionallowing aggregate particles to remain suspended in the cementitiouscomposition without segregation when subjected to normal movementassociated with transportation, pumping, placing, and consolidation byvibration. Nevertheless, all these traditional suspending aids haveadverse effects such as impairing the initial workability by increasingwater demand and/or viscosity, retarding the setting and hardening offresh mixes, entraining air, and reducing flow retention.

[0007] Therefore, it is desirable to provide an admixture formulationthat stabilizes the rheology by reducing bleeding and separation of acementitious composition without adversely affecting workability,setting, strength and other performance properties.

SUMMARY

[0008] An admixture formulation for cementitious compositions isprovided that comprises at least one polycarboxylate dispersant combinedwith at least one naphthalene dispersant, wherein the amount ofpolycarboxylate dispersant is about 1% to about 99% and the amount ofnaphthalene dispersant is about 1% to about 99% based on the weight ofdry solids. The admixture formulation improves bleeding resistance andreduces segregation in cementitious compositions without producing manyof the undesirable side-effects.

[0009] A cementitious composition is provided that comprises hydrauliccement, at least one polycarboxylate dispersant and at least onenaphthalene dispersant, wherein the amount of polycarboxylate dispersantis about 0.001% to about 10% primary active ingredient and the amount ofnaphthalene dispersant is about 0.001% to about 10% primary activeingredient based on the total dry weight of cementitious material.

[0010] A method is provided for making a cementitious compositioncomprising forming a mixture of water, hydraulic cement, an amount ofabout 0.001% to about 10% primary active ingredient of polycarboxylatedispersant, and an amount about 0.001% to about 10% primary activeingredient of naphthalene dispersant based on the total dry weight ofcementitious material.

DETAILED DESCRIPTION

[0011] A dry or liquid admixture formulation of polycarboxylatecopolymer and naphthalene dispersant is provided that controls bleed andsegregation in flowable and/or fluid cementitious compositions such asmortars, grouts, toppings and concrete. A cementitious compositioncontaining the admixture formulation is also provided as well as a novelmethod for preparing such a cementitious composition.

[0012] It has now been discovered that an appropriate combination ofnaphthalene dispersant and polycarboxylate-based polymer provides a morestable cementitious composition with better flow, and little or no waterloss or segregation. Furthermore, this new combination does not affectsetting and hardening of cementitious compositions. Additionally, anair-entraining agent can be used that improves the plasticity ofcementitious compositions and supplements the sand suspension, as thesmall, stable bubbles entrained in the mixture act like flexible ballbearings. The combination of certain naphthalene dispersants,polycarboxylate dispersant and optionally air-entraining agents provideslower pump pressure, increased fluidity, reduced bleeding andsegregation, reduction in internal friction and better setting andhardening features.

[0013] Contrary to what is shown in the prior art, that the combinationof polycarboxylate dispersant and naphthalene dispersant causesunacceptable gelling by increasing flocculation, we discovered that whenpolycarboxylate dispersants and naphthalene dispersants are combined atvarious levels, they interact synergistically to reduce the tendency forbleed and segregation in cementitious mixtures. The present admixtureformulation is an improvement over prior art thickeners or rheologymodifiers such as cellulose ethers, silica fume, polyacrylamides,polysaccharides, water soluble gums, and clays, in that it does notincrease water demand, retard setting, entrain air, increase watersensitivity, promote high viscosity, or reduce flow retention asobserved with the prior art thickening agents.

[0014] Thickening agents or rheology modifiers are commonly used toaddress bleeding, sedimentation, segregation and deflocculation incementitious compositions. Their principle mechanism is an increase inviscosity brought about by the formation of gelled aqueous phases orincreased inter-particle attraction from associative or ionic bonding.Depending on the type of thickener used, the time dependency of theshear, the shear rate, and the shear stress; the rheological behavior ofthe mixture can be Newtonian, Non-Newtonian, viscoelastic, dilatent,pseudoplastic, thixotropic, or rheopectic. Most conventionalthickeners/rheology modifiers will significantly increase viscosity andwater demand, as well as affect rheological properties that are notdesirable with fluid and/or flowable compositions.

[0015] Without being limited to theory, it is thought that thesynergistic mechanism between naphthalene dispersants andpolycarboxylate dispersants is brought about when highly chargedsulfonic groups from a naphthalene dispersant, such as those ofnaphthalene sulfonate formaldehyde condensate, interact with thepolyether side chains of the polycarboxylate, causing the cementparticles to flocculate. The degree of flocculation and resultinggelation/thickening may be affected by the dosage and the molecularweight of the polycarboxylate dispersant. The longer the ether sidechains, the more pronounced the effect.

[0016] The naphthalene dispersants used can be any suitable naphthalenedispersant such as naphthalene sulfonate formaldehyde condensate, betanaphthalene sulfonates, or sodium naphthalene sulfate formaldehydecondensate resins, for example LOMAR D® (Cognis Inc., Cincinnati, Ohio).

[0017] Some non-polycarboxylate dispersants such as oligomerics,melamine formaldehyde condensate resins, salts of melamine formaldehydecondensate resins, carboxylic acids, salts of carboxylic acids, calciumlignosulfonates, and mixtures thereof do not demonstrate the rheologymodifying effects found with naphthalene dispersants. These unaffectednon-polycarboxylate dispersants can be used as normal water reducingadditives.

[0018] In one embodiment, the admixture formulation contains about 1% toabout 99% of a naphthalene dispersant based on the total dry weight ofthe admixture formulation. In another embodiment, the admixtureformulation contains about 5% to about 95% naphthalene dispersant basedon the total dry weight of the admixture formulation. In a furtherembodiment, the admixture formulation contains about 10% to about 90%naphthalene dispersant based on the total dry weight of the admixtureformulation. In certain embodiments, a cementitious composition containsabout 0.001% to about 10% naphthalene dispersant based on the total dryweight of cementitious material. In further embodiments a cementitiouscomposition contains about 0.01% to about 5% naphthalene dispersantbased on the total dry weight of cementitious material. In anotherembodiment a cementitious composition contains about 0.1% to about 2%naphthalene dispersant based on the total dry weight of cementitiousmaterial.

[0019] Polycarboxylate dispersants are dispersants having a carbonbackbone with pendant side chains, wherein at least a portion of theside chains are attached to the backbone through a carboxyl group or anether group. The term dispersant is also meant to include thosechemicals that also function as a plasticizer, high range water reducer,fluidizer, antiflocculating agent, or superplasticizer for cementitiouscompositions. Examples of polycarboxylate dispersants can be found inU.S. Pat. No. 6,310,143, U.S. Pat. Nos. 6,290,770, 6,267,814, U.S. Pat.No. 6,211,317, U.S. Pat. No. 6,187,841, U.S. Pat. No. 5,158,996, U.S.Pat. No. 6,008,275, U.S. Pat. No. 6,136,950, U.S. Pat. No. 6,284,867,U.S. Pat. No. 5,609,681, U.S. Pat. No. 5,494,516; U.S. Pat. No.5,674,929, U.S. Pat. No. 5,660,626, U.S. Pat. No. 5,668,195, U.S. Pat.No. 5,661,206, U.S. Pat. No. 5,358,566, U.S. Pat. No. 5,162,402, U.S.Pat. No. 5,798,425, U.S. Pat. No. 5,612,396, U.S. Pat. No. 6,063,184,and U.S. Pat. No. 5,912,284, U.S. Pat. No. 5,840,114, U.S. Pat. No.5,753,744, U.S. Pat. No. 5,728,207, U.S. Pat. No. 5,725,657, U.S. Pat.No. 5,703,174, U.S. Pat. No. 5,665,158, U.S. Pat. No. 5,643,978, U.S.Pat. No. 5,633,298, U.S. Pat. No. 5,583,183, and U.S. Pat. No.5,393,343, which are incorporated herein by reference. Thepolycarboxylate high range water reducing dispersants used in theadmixture formulation of the present invention may include but are notlimited to dispersants or water reducers sold under the trademarksMELFLUX® 1643F and 1641 (SKW Polymers), FC600 (Nippon Shokubai), SD 100(Takemoto Oil & Fat CO., LTD), Daxad 30S (Hampshire Chemical Corp.), andShokanal DS3557 (BASF).

[0020] In one embodiment, the admixture formulation contains about 1% toabout 99% polycarboxylate dispersant based on the total dry weight ofthe admixture formulation. In another embodiment, the admixtureformulation contains about 5% to about 95% polycarboxylate dispersantbased on the total dry weight of the admixture formulation. In a furtherembodiment, the admixture formulation contains about 10% to about 90%polycarboxylate dispersant based on the total dry weight of theadmixture formulation. In certain embodiments a cementitious compositioncontains about 0.001% to about 10% polycarboxylate dispersant based onthe total dry weight of cementitious material. In a further embodiment acementitious composition contains about 0.01% to about 5%polycarboxylate dispersant based on the dry weight of cementitiousmaterial. In another embodiment a cementitious composition containsabout 0.1% to about 2% polycarboxylate dispersant based on the dryweight of cementitious material.

[0021] The polycarboxylate dispersants used in combination with thenaphthalene dispersants are at least one of

[0022] a) a dispersant of Formula (I):

[0023] wherein in Formula (I)

[0024] X is at least one of hydrogen, an alkali earth metal ion, analkaline earth metal ion, ammonium ion, or amine;

[0025] R is at least one of C₁ to C₆ alkyl(ene)ether or mixtures thereofor C₁ to C₆ alkyl(ene)imine or mixtures thereof;

[0026] Q is at least one of oxygen, NH, or sulfur;

[0027] p is a number from 1 to about 300 resulting in at least one of alinear side chain or branched side chain;

[0028] R₁ is at least one of hydrogen, C₁ to C₂₀ hydrocarbon, orfunctionalized hydrocarbon containing at least one of —OH, —COOH, anester or amide derivative of —COOH, sulfonic acid, an ester or amidederivative of sulfonic acid, amine, or epoxy;

[0029] Y is at least one of hydrogen, an alkali earth metal ion, analkaline earth metal ion, ammonium ion, amine, a hydrophobic hydrocarbonor polyalkylene oxide moiety that functions as a defoamer;

[0030] m, m′, m″, n, n′, and n″ are each independently 0 or an integerbetween 1 and about 20;

[0031] Z is a moiety containing at least one of i) at least one amineand one acid group, ii) two functional groups capable of incorporatinginto the backbone selected from the group consisting of dianhydrides,dialdehydes, and di-acid-chlorides, or iii) an imide residue; and

[0032] wherein a, b, c, and d reflect the mole fraction of each unitwherein the sum of a, b, c, and d equal one, wherein a, b, c, and d areeach a value greater than or equal to zero and less than one, and atleast two of a, b, c, and d are greater than zero;

[0033] b) a dispersant of Formula (II):

[0034] wherein in Formula (II):

[0035] A is COOM or optionally in the “y” structure an acid anhydridegroup (—CO—O—CO—) is formed in place of the A groups between the carbonatoms to which the A groups are bonded to form an anhydride;

[0036] B is COOM;

[0037] M is hydrogen, a transition metal cation, the residue of ahydrophobic polyalkylene glycol or polysiloxane, an alkali metal ion, analkaline earth metal ion, ferrous ion, aluminum ion, (alkanol)ammoniumion, or (alkyl)ammonium ion;

[0038] R is a C₂₋₆ alkylene radical;

[0039] R1 is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group;

[0040] x, y, and z are a number from 0.01 to 100;

[0041] m is a number from 1 to 100; and

[0042] n is a number from 10 to 100;

[0043] c) a dispersant comprising at least one polymer or a salt thereofhaving the form of a copolymer of

[0044] i) a maleic anhydride half-ester with a compound of the formulaRO(AO)_(m)H, wherein R is a C₁-C₂₀ alkyl group, A is a C₂₋₄ alkylenegroup, and m is an integer from 2-16; and

[0045] ii) a monomer having the formula CH₂═CHCH₂—(OA)_(n)OR, wherein nis an integer from 1-90 and R is a C₁₋₂₀ alkyl group;

[0046] d) a dispersant obtained by copolymerizing 5 to 98% by weight ofan (alkoxy)polyalkylene glycol mono(meth)acrylic ester monomer (a)represented by the following general formula (1):

[0047] wherein R₁ stands for hydrogen atom or a methyl group, R₂O forone species or a mixture of two or more species of oxyalkylene group of2 to 4 carbon atoms, providing two or more species of the mixture may beadded either in the form of a block or in a random form, R₃ for ahydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m is a valueindicating the average addition mol number of oxyalkylene groups that isan integer in the range of 1 to 100, 95 to 2% by weight of a(meth)acrylic acid monomer (b) represented by the above general formula(2), wherein R₄ and R₅ are each independently a hydrogen atom or amethyl group, and M₁ for a hydrogen atom, a monovalent metal atom, adivalent metal atom, an ammonium group, or an organic amine group, and 0to 50% by weight of other monomer (c) copolymerizable with thesemonomers, provided that the total amount of (a), (b), and (c) is 100% byweight;

[0048] e) a graft polymer that is a polycarboxylic acid or a saltthereof, having side chains derived from at least one species selectedfrom the group consisting of oligoalkyleneglycols, polyalcohols,polyoxyalkylene amines, and polyalkylene glycols;

[0049] f) a dispersant of Formula (III):

[0050] wherein in Formula (III):

[0051] D=a component selected from the group consisting of the structured1, the structure d2, and mixtures thereof;

[0052] X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or SulfonatedPhenyl;

[0053] Y=H or —COOM;

[0054] R=H or CH₃;

[0055] Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃,or —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃, —CONHC(CH₃)₂ CH₂SO₃M,—COO(CHR4)_(n)OH where n=2 to 6, or —O(CH₂)_(n)OR₄ wherein n=2 to 6;

[0056] R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄ randomcopolymer of oxyethylene units and oxypropylene units where m=10 to 500and wherein the amount of oxyethylene in the random copolymer is fromabout 60% to 100% and the amount of oxypropylene in the random copolymeris from 0% to about 40%;

[0057] R₄=H, Methyl, C₂ to about C₆ Alkyl, or about C₆ to about C₁₀aryl;

[0058] M=H, Alkali Metal, Alkaline Earth Metal, Ammonium, Amine,triethanol amine, Methyl, or C₂ to about C₆ Alkyl;

[0059] a=0 to about 0.8;

[0060] b=about 0.2 to about 1.0;

[0061] c=0 to about 0.5;

[0062] d=0 to about 0.5; and

[0063] wherein a, b, c, and d represent the mole fraction of each unitand the sum of a, b, c, and d is 1.0;

[0064] g) a dispersant of Formula (IV):

[0065] wherein in Formula (IV): the “b” structure is one of a carboxylicacid monomer, an ethylenically unsaturated monomer, or maleic anhydridewherein an acid anhydride group (—CO—O—CO—) is formed in place of thegroups Y and Z between the carbon atoms to which the groups Y and Z arebonded respectively, and the “b” structure must include at least onemoiety with a pendant ester linkage and at least one moiety with apendant amide linkage;

[0066] X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, p-EthylPhenyl, Carboxylated Phenyl, or Sulfonated Phenyl;

[0067] Y=H, —COOM, —COOH, or W;

[0068] W=a hydrophobic defoamer represented by the formulaR₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s, t, and u areintegers from 0 to 200 with the proviso that t>(s+u) and wherein thetotal amount of hydrophobic defoamer is present in an amount less thanabout 10% by weight of the polycarboxylate dispersant;

[0069] Z=H, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, —(CH₂)_(n)OR₃where n=0 to 6, or —CONHR₃;

[0070] R=H, or CH₃;

[0071] R₂, R₃, are each independently a random copolymer of oxyethyleneunits and oxypropylene units of the general formula —(CH(R₁)CH₂O)_(m)R₄where m=10 to 500 and wherein the amount of oxyethylene in the randomcopolymer is from about 60% to 100% and the amount of oxypropylene inthe random copolymer is from 0% to about 40%;

[0072] R₄=H, Methyl, or C₂ to C₈ Alkyl;

[0073] R₅=C₁ to C₁₈ alkyl or C₆ to C₁₈ alkyl aryl;

[0074] M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine, monoethanolamine, diethanol amine, triethanol amine, morpholine, imidazole;

[0075] a=0.01-0.8;

[0076] b=0.2-0.99;

[0077] c=0-0.5; and

[0078] wherein a, b, c represent the mole fraction of each unit and thesum of a, b, and c, is 1;

[0079] h) a random copolymer corresponding to the following Formula (V)in free acid or salt form having the following monomer units and numbersof monomer units:

[0080] wherein A is selected from the moieties (i) or (ii)

[0081] (i) —CR₁R₂—CR₃R₄—

[0082] wherein R₁ and R₃ are selected from substituted benzene, C₁₋₈alkyl, C₂-8 alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy, carboxyl,hydrogen, and a ring, R₂ and R₄ are selected from the group consistingof hydrogen and C₁₋₄ alkyl, wherein R₁ and R₃ can together with R₂and/or R₄ when R₂ and/or R₄ are C₁₋₄ alkyl form the ring;

[0083] R₇, R₈, R₉, and R₁₀ are individually selected from the groupconsisting of hydrogen, C₁₋₆ alkyl, and a C₂₋₈ hydrocarbon chain,wherein R₁ and

[0084] R₃ together with R₇ and/or R₈, R₉, and R₁₀ form the C₂₋₈hydrocarbon chain joining the carbon atoms to which they are attached,the hydrocarbon chain optionally having at least one anionic group,wherein the at least one anionic group is optionally sulfonic; M isselected from the group consisting of hydrogen, and the residue of ahydrophobic polyalkylene glycol or a polysiloxane, with the proviso thatwhen A is (ii) and M is the residue of a hydrophobic polyalkyleneglycol, M must be different from the group —(R₅O)_(m)R₆;

[0085] R₅ is a C₂₋₈ alkylene radical;

[0086] R₆ is selected from the group consisting of C₁₋₂₀ alkyl, C₆₋₉cycloalkyl and phenyl;

[0087] n, x, and z are numbers from 1 to 100;

[0088] y is 0 to 100;

[0089] m is 2 to 1000;

[0090] the ratio of x to (y+z) is from 1:10 to 10:1 and the ratio of y:zis from 5:1 to 1:100;

[0091] i) a copolymer of oxyalkyleneglycol-alkenyl ethers andunsaturated dicarboxylic acids, comprising:

[0092] i) 0 to 90 mol % of at least one component of the formula 3a or3b:

[0093] wherein M is a hydrogen atom, a mono- or divalent metal cation,an ammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½;

[0094] wherein X is —OM_(a),

[0095] —O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100,

[0096] —NHR₂, —N(R²)₂ or mixtures thereof in which R²═R¹ or —CO—NH₂; and

[0097] wherein Y is an oxygen atom or —NR₂;

[0098] ii) 1 to 89 mol % of components of the general formula 4:

[0099] wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon radicalcontaining from 1 to 5 carbon atoms, p is 0 to 3, and R₁ is hydrogen, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonic substituted arylradical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,and

[0100] iii) 0.1 to 10 mol % of at least one component of the formula 5aor 5b:

[0101] wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is —COOR₅,—W—R₇, —CO—[—NH—(CH₂)₃)—]_(s)—W—R₇, —CO—O—(CH₂)_(z)—W—R₇, a radical ofthe general formula:

[0102] or —(CH₂)_(z)—V—(CH₂)₂—CH═CH—R₁, or when S is —COOR₅ or—COOM_(a), U₁ is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O— or —OCH₂, Vis —O—CO—C₆H₄—CO—O— or —W—, and W is

[0103] R4 is a hydrogen atom or a methyl radical, R5 is an aliphatichydrocarbon radical containing 3 to 20 carbon atoms, a cycloaliphatichydrocarbon radical containing 5 to 8 carbon atoms or an aryl radicalcontaining 6 to 14 carbon atoms, R₆═R₁ or

[0104] R₇═R₁ or

[0105] r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and z is0 to 4;

[0106] iv) 0 to 90 mol % of at least one component of the formula 6a,6b, or 6c:

[0107] wherein M is a hydrogen atom, a mono- or divalent metal cation,an ammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½;

[0108] wherein X is —OM_(a),

[0109] —O—(C_(m)H_(2m)O)_(n)—R₁ in which R¹ is a hydrogen atom, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100,

[0110] —NH—(C_(m)H_(2m)O)_(n)—R¹,

[0111] —NHR₂, —N(R²)₂ or mixtures thereof in which R²═R¹ or —CO—NH₂; and

[0112] wherein Y is an oxygen atom or —NR²;

[0113] j) a copolymer of dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, comprising:

[0114] i) 1 to 90 mol. % of at least one member selected from the groupconsisting of structural units of Formula 7a and Formula 7b:

[0115] wherein M is H, a monovalent metal cation, a divalent metalcation, an ammonium ion or an organic amine;

[0116] a is ½ when M is a divalent metal cation or 1 when M is amonovalent metal cation;

[0117] wherein R¹ is —OM_(a), or

[0118] —O—(C_(m)H_(2m)O)_(n)—R² wherein R is H, a C₁₋₂₀ aliphatichydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2);

[0119] m is 2 to 4;

[0120] n is 1 to 200;

[0121] ii) 0.5 to 80 mol. % of the structural units of Formula 8:

[0122] wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon;

[0123] p is 0 to 3;

[0124] R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatichydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted with atleast one member selected from the group consisting of —COOM_(a),—(SO₃)M_(a), and —(PO₃)M_(a2);

[0125] m is 2 to 4;

[0126] n is 1 to 200;

[0127] iii) 0.5 to 80 mol. % structural units selected from the groupconsisting of Formula 9a and Formula 9b:

[0128] wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is optionallysubstituted with at least one hydroxyl group, —(C_(m)H_(2m)O)_(n)—R²,—CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2);

[0129] M is H, a monovalent metal cation, a divalent metal cation, anammonium ion or an organic amine;

[0130] a is ½ when M is a divalent metal cation or 1 when M is amonovalent metal cation;

[0131] R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatichydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted with atleast one member selected from the group consisting of —COOM_(a),—(SO₃)M_(a), and —(PO₃)M_(a2);

[0132] m is 2 to 4;

[0133] n is 1 to 200;

[0134] iv) 1 to 90 mol. % of structural units of Formula 10

[0135] wherein R⁵ is methyl, or methylene group, wherein R⁵ forms one ormore 5 to 8 membered rings with R⁷;

[0136] R⁶ is H, methyl, or ethyl;

[0137] R⁷ is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2), a C₅₋₈cycloaliphatic hydrocarbon, —OCOR⁴, —OR⁴, or —COOR⁴, wherein R⁴ is H, aC₁₋₂₀ aliphatic hydrocarbon that is optionally substituted with at leastone —OH, —(C_(m)H_(2m)O)_(n)—R₂, —CO—NH—R², C₅₋₈ cycloaliphatichydrocarbon, or a C₆₋₁₄ aryl residue that is optionally substituted witha member selected from the group consisting of —COOM_(a), —(SO₃)M_(a),—(PO₃)M_(a2).

[0138] In formula (e) the word “derived” does not refer to derivativesin general, but rather to any polycarboxylic acid/salt side chainderivatives of oligoalkyleneglycols, polyalcohols, polyoxyalkyleneamines, and polyalkylene glycols that are compatible with dispersantproperties and do not destroy the graft polymer.

[0139] The preferred substituents in the optionally substituted aryl offormula (j), containing 6 to 14 carbon atoms, are hydroxyl, carboxyl,C₁₋₁₄ alkyl, or sulfonate groups.

[0140] The preferred substituents in formula (h) in the substitutedbenzene are hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonate groups.

[0141] In certain embodiments, the suspending effect and some of thedispersing effect is caused by the naphthalene/polycarboxylateinteraction and the balance of the dispersing effect is caused by anunaffected non-polycarboxylate dispersant such as oligomerics, melamineformaldehyde condensate resins, salts of melamine formaldehydecondensate resins, carboxylic acids, salts of carboxylic acids, calciumlignosulfonates, and mixtures thereof. The level of the unaffectednon-polycarboxylate dispersant can be adjusted to control theflowability of the cementitious mixture, wherein the unaffectednon-polycarboxylate dispersant is added without affecting the suspendingability of the polycarboxylate/naphthalene interaction.

[0142] The term oligomeric dispersant throughout this specificationrefers to oligomers that are a reaction product of a component A,optionally component B, and component C that are described in U.S. Pat.No. 6,133,347, U.S. Pat. No. 6,451,881, U.S. Ser. No. 09/629,724 filedon Jul. 31, 2000, and U.S. Ser. No. 10/244,253 filed on Sep. 16, 2002,which are hereby incorporated by reference.

[0143] The oligomeric dispersants are a reaction product of component A,optionally component B, and component C;

[0144] wherein each component A is independently a nonpolymeric,multi-functional moiety or combination of mono or multifunctionalmoieties that adsorbs onto a cementitious particle, and contains atleast one residue derived from a first component selected from the groupconsisting of phosphates, phosphonates, phosphinates, hypophosphites,sulfates, sulfonates, sulfinates, alkyl trialkoxy silanes, alkyltriacyloxy silanes, alkyl triaryloxy silanes, borates, boronates,boroxines, phosphoramides, amines, amides, quaternary ammonium groups,carboxylic acids, carboxylic acid esters, alcohols, carbohydrates,phosphate esters of sugars, borate esters of sugars, sulfate esters ofsugars, salts of any of the preceding moieties, and mixtures thereof;

[0145] wherein component B is an optional moiety, where if present, eachcomponent B is independently a nonpolymeric moiety that is disposedbetween the component A moiety and the component C moiety, and isderived from a second component selected from the group consisting oflinear saturated hydrocarbons, linear unsaturated hydrocarbons,saturated branched hydrocarbons, unsaturated branched hydrocarbons,alicyclic hydrocarbons, heterocyclic hydrocarbons, aryl, phosphoester,nitrogen containing compounds, and mixtures thereof; and

[0146] wherein component C is at least one moiety that is a linear orbranched water soluble, nonionic polymer substantially non-adsorbing tocement particles, and is selected from the group consisting ofpoly(oxyalkylene glycol), poly(oxyalkylene amine), poly(oxyalkylenediamine), monoalkoxy poly(oxyalkylene amine), monoaryloxypoly(oxyalkylene amine), monoalkoxy poly(oxyalkylene glycol),monoaryloxy poly(oxyalkylene glycol), poly(vinyl pyrrolidones),poly(methyl vinyl ethers), poly(ethylene imines), poly(acrylamides),polyoxazoles, and mixtures thereof.

[0147] The term air entrainer includes any chemical that will entrainair in cementitious compositions. Air entrainers can also reduce thesurface tension of a composition at low concentration. Air-entrainingadmixtures are used to purposely entrain microscopic air bubbles intoconcrete. Air-entrainment dramatically improves the durability ofconcrete exposed to moisture during cycles of freezing and thawing. Inaddition, entrained air greatly improves a concrete's resistance tosurface scaling caused by chemical deicers. Air entrainment alsoincreases the workability of fresh concrete while eliminating orreducing segregation and bleeding.

[0148] Air entraining materials used to achieve these desired effectscan be selected from wood resin, sulfonated lignin, petroleum acids,proteinaceous material, fatty acids, resinous acids, alkylbenzenesulfonates, sulfonated hydrocarbons, vinsol resin, anionic surfactants,cationic surfactants, nonionic surfactants, natural rosin, syntheticrosin, an inorganic air entrainer, synthetic detergents, and theircorresponding salts, and mixtures thereof. If air entrainers are to beused they are added in an amount to yield a desired level of air in acementitious composition and can be any known air entrainer for cement,including natural resin, synthetic resin, and mixtures thereof

[0149] Cementitious materials are materials that alone have hydrauliccementing properties, and set and harden in the presence of water.Included in cementitious materials are ground granulated blast-furnaceslag, natural cement, portland cement, modified portland cement, masonrycement, hydraulic hydrated lime, and combinations of these and othermaterials. By portland cement is meant a hydraulic cement produced bypulverizing clinker, comprising hydraulic calcium silicates, calciumaluminates, and calcium aluminoferrites, and usually containing one ormore of the forms of calcium sulfate as an interground addition, andincludes portland cement, the specification for which is set forth inASTM specification C 150, and cements that are chemically similar oranalogous to portland cement, the specifications for which are set forthin ASTM specifications C 1157, C 595, and C 845.

[0150] Aggregate can be included in the cementitious formulation toprovide for mortars which include fine aggregate, and concretes whichalso include coarse aggregate. The fine aggregates are materials thatpass through a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silicasand. The coarse aggregate are materials that are retained on a Number 4sieve (ASTM C 125 and ASTM C 33), such as silica, quartz, crushed roundmarble, glass spheres, granite, limestone, calcite, feldspar, alluvialsands, sands or any other durable aggregate, and mixtures thereof. Othertypes of aggregates can also be used such as metallic particles, heavyweight aggregates, and light weight aggregates such as described in ASTMstandards C 330, C 331, C 332 and ACI International 211.2R, 313R,304.5R, 304.3R, and 221R.

[0151] The bleeding resistance and segregation reduction admixtureformulation may comprise other additives or ingredients and should notbe limited to the stated formulations. Cement additives that can beadded include, but are not limited to: set accelerators, set retarders,air-entraining or air detraining agents, water reducer, corrosioninhibitors, pigments, wetting agents, water soluble polymers, rheologymodifying agents, water repellents, fibers, dampproofing admixtures, gasformers, permeability reducers, pumping aids, fungicidal admixtures,germicidal admixtures, insecticidal admixtures, finely divided mineraladmixtures, alkali-reactivity reducer, bonding admixtures, strengthenhancing agents, shrinkage reducing agents, and any other admixture oradditive that does not adversely affect the properties of the bleedingresistance and segregation reduction admixture formulation.

[0152] A set accelerator, if used in the bleeding resistance andsegregation reduction admixture formulation, can include, but is notlimited to, a nitrate salt of an alkali metal, alkaline earth metal, oraluminum; a nitrite salt of an alkali metal, alkaline earth metal, oraluminum; a thiocyanate of an alkali metal, alkaline earth metal oraluminum; an alkanolamine; a thiosulphate of an alkali metal, alkalineearth metal, or aluminum; a hydroxide of an alkali metal, alkaline earthmetal, or aluminum; a carboxylic acid salt of an alkali metal, alkalineearth metal, or aluminum (preferably calcium formate); apolyhydroxylalkylamine; or a halide salt of an alkali metal or alkalineearth metal (preferably bromide).

[0153] The salts of nitric acid have the general formula M(NO₃)_(a)where M is an alkali metal , or an alkaline earth metal or aluminum, andwhere a is 1 for alkali metal salts, 2 for alkaline earth salts, and 3for aluminum salts. Preferred are nitric acid salts of Na, K, Mg, Ca andAl.

[0154] Nitrite salts have the general formula M(NO₂)_(a) where M is analkali metal, or an alkaline earth metal or aluminum, and where a is 1for alkali metal salts, 2 for alkaline earth salts, and 3 for aluminumsalts. Preferred are nitric acid salts of Na, K, Mg, Ca and Al.

[0155] The salts of the thiocyanic acid have the general formulaM(SCN)_(b)

[0156] , where M is an alkali metal, or an alkaline earth metal oraluminum, and where b is 1 for alkali metal salts, 2 for alkaline earthsalts and 3 for aluminum salts. These salts are variously known assulfocyanates, sulfocyanides, rhodanates or rhodanide salts. Preferredare thiocyanic acid salts of Na, K, Mg, Ca and Al.

[0157] Alkanolamine is a generic term for a group of compounds in whichtrivalent nitrogen is attached directly to a carbon atom of an alkylalcohol. A representative formula is N[H]_(c)[(CH₂)_(d)CH₂OH]_(e), wherec is 3-e, d is 1 to about 5 and e is 1 to about 3. Examples include, butare not limited to, are monoethanoalamine, diethanolamine andtriethanolamine.

[0158] The thiosulfate salts have the general formula M_(f)(S₂O₃)_(g)where M is alkali metal or an alkaline earth metal or aluminum, and f is1 or 2 and g is 1, 2 or 3, depending on the valencies of the M metalelements. Preferred are thiosulfate acid salts of Na, K, Mg, Ca and Al.

[0159] The carboxylic acid salts have the general formula RCOOM whereinR is H or C₁ to about C₁₀ alkyl, and M is alkali metal or an alkalineearth metal or aluminum. Preferred are carboxylic acid salts of Na, K,Mg, Ca and Al. In one embodiment the carboxylic acid salt is calciumformate.

[0160] In one embodiment polyhydroxylalkylamine has the general formula

[0161] wherein h is 1 to 3, i is 1 to 3, j is 1 to 3, and k is 0 to 3. Apreferred polyhydroxyalkylamine is tetrahydroxyethylethylenediamine.

[0162] Retarding, or delayed-setting, admixtures are used to retard,delay, or slow the rate of setting of concrete. They can be added to theconcrete mix upon initial batching or sometime after the hydrationprocess has begun. Retarders are commonly used to offset theaccelerating effect of hot weather on the setting of concrete, to delaythe initial set of concrete or grout when difficult conditions ofplacement occur or problems of delivery to the job site, to allow timefor special finishing processes or to aid in the reclamation of concreteleft over at the end of the work day. Most retarders also act as waterreducers and can also be used to entrain some air into concrete.

[0163] The retarder can include but is not limited to an oxy-boroncompound, lignin, a polyphosphonic acid, a carboxylic acid, ahydroxycarboxylic acid, polycarboxylic acid, hydroxylated carboxylicacid, fumaric, itaconic, malonic, borax, gluconic, and tartaric acid,lignosulfonates, ascorbic acid, isoascorbic acid, sulphonic acid-acrylicacid copolymer, and their corresponding salts, polyhydroxysilane,polyacrylamide, carbohydrates and mixtures thereof. Illustrativeexamples of retarders are set forth in U.S. Pat. Nos. 5,427,617 and5,203,919, incorporated herein by reference.

[0164] Air detrainers are used to decrease the air content in thecementitious composition. Examples of air detrainers that can beutilized include, but are not limited to tributyl phosphate, dibutylphthalate, octyl alcohol, water-insoluble esters of carbonic and boricacid, acetylenic diols, ethylene oxide-propylene oxide block copolymers,lignosulfonates, hydroxylated carboxylic acids, lignin, borax, gluconic,tartaric and other organic acids and their corresponding salts,phosphonates, certain carbohydrates and silicones.

[0165] Corrosion inhibitors in concrete serve to protect embeddedreinforcing steel from corrosion. The high alkaline nature of theconcrete causes a passive and noncorroding protective oxide film to formon the steel. However, carbonation or the presence of chloride ions fromdeicers or seawater, together with oxygen can destroy or penetrate thefilm and result in corrosion. Corrosion-inhibiting admixtures chemicallyslow this corrosion reaction. The materials most commonly used toinhibit corrosion are calcium nitrite, sodium nitrite, sodium benzoate,certain phosphates or fluorosilicates, fluoroaluminates, amines, organicbased water repelling agents, and related chemicals.

[0166] Dampproofing admixtures reduce the permeability of concrete thathas low cement contents, high water-cement ratios, or a deficiency offines in the aggregate portion. These admixtures retard moisturepenetration into dry concrete and include certain soaps, stearates,waxes, and petroleum products.

[0167] Permeability reducers are used to reduce the rate at which waterunder pressure is transmitted through concrete. Silica fume, fly ash,ground slag, metakaolin, natural pozzolans, water reducers, and latexcan be employed to decrease the permeability of the concrete.

[0168] Pumping aids are added to concrete mixes to improve pumpability.These admixtures thicken the fluid concrete, i.e., increase itsviscosity, to reduce de-watering of the paste while it is under pressurefrom the pump. Among the materials used as pumping aids in concrete areorganic and synthetic polymers, hydroxyethylcellulose (HEC) or HECblended with dispersants, organic flocculents, organic emulsions ofparaffin, coal tar, asphalt, acrylics, bentonite and pyrogenic silicas,natural pozzolans, fly ash and hydrated lime.

[0169] Bacteria and fungal growth on or in hardened concrete may bepartially controlled through the use of fungicidal, germicidal, andinsecticidal admixtures. The most effective materials for these purposesare polyhalogenated phenols, dialdrin emulsions, and copper compounds.

[0170] Finely divided mineral admixtures are materials in powder orpulverized form added to concrete before or during the mixing process toimprove or change some of the plastic or hardened properties of portlandcement concrete. The finely divided mineral admixtures can be classifiedaccording to their chemical or physical properties as: cementitiousmaterials; pozzolans; pozzolanic and cementitious materials; andnominally inert materials.

[0171] A pozzolan is a siliceous or aluminosiliceous material thatpossesses little or no cementitious value but will, in the presence ofwater and in finely divided form, chemically react with the calciumhydroxide produced during the hydration of portland cement to formmaterials with cementitious properties. Diatomaceous earth, opalinecherts, clays, shales, fly ash, silica fume, volcanic tuffs andpumicites are some of the known pozzolans. Natural pozzolan is a term ofart used to define the pozzolans that occur in nature, such as volcanictuffs, pumices, trasses, diatomaceous earths, opaline, cherts, and someshales. Fly ash is defined in ASTM C618.

[0172] Alkali-reactivity reducers can reduce the alkali-aggregatereaction and limit the disruptive expansion forces that this reactioncan produce in hardened concrete. Pozzolans (fly ash, silica fume),blast-furnace slag, salts of lithium and barium are especiallyeffective.

[0173] Bonding admixtures are usually added to portland cement mixturesto increase the bond strength between old and new concrete and includeorganic materials such as rubber, polyvinyl chloride, polyvinyl acetate,acrylics, styrene butadiene copolymers, and other powdered polymers.

[0174] In the construction field, many methods of protecting concretefrom tensile stresses and subsequent cracking have been developedthrough the years. One modern method involves distributing fibersthroughout a fresh concrete mixture. Upon hardening, this concrete isreferred to as fiber-reinforced concrete. Fibers can be made ofzirconium materials, carbon, steel, fiberglass, or synthetic materials,e.g., polypropylene, nylon, polyethylene, polyester, rayon,high-strength aramid, or mixtures thereof.

[0175] A shrinkage reducing agent which can be used in the cementitiouscomposition may include but is not limited to RO(AO)₁₋₁₀H, wherein R isa C₁₋₅ alkyl or C₅₋₆ cycloalkyl radical and A is a C₂₋₃ alkyleneradical, alkali metal sulfate, alkaline earth metal sulfates, alkalineearth oxides, preferably sodium sulfate and calcium oxide. TETRAGUARDPW® shrinkage reducing agent is preferred and is available from-MasterBuilders Inc. of Cleveland, Ohio.

[0176] Natural and synthetic admixtures are used to color concrete foraesthetic and safety reasons. These coloring admixtures are usuallycomposed of pigments and include carbon black, iron oxide,phthalocyanine, umber, chromium oxide, titanium oxide and cobalt blue.

EXAMPLES

[0177] The samples in Tables 1-5 were prepared using a dry mixture thatcomprised cementitious binder, polycarboxylate high range water reducingdispersant, sulfonated naphthalene-formaldehyde condensate, andadditives. The dry mixture was added to water and mixed for about 4minutes in a Hobart paddle mixer. After mixing, static bleed,workability, flow, and segregation were measured.

[0178] Table 1 summarizes the bleed amount of water of sample pastesthat comprised 1500 gm of Type I/II Portland cement and had an initialvolume of 800 ml. The bleed amount of the pastes was determined inaccordance with ASTM C 940. TABLE 1 Sample S1 S2 S3 S4 SNF (gm) 11.2511.25 — 6.0 PC (gm) 6.75 11.25 11.25 W/C ratio 0.5 0.5 0.40 0.40 Volumeof Bleed Water (ml) ½ hr 40 10 20 10   1 hr 50 13 20 10 1.5 hr 60 20 3010   2 hr 70 20 30 10

[0179] Table 1 demonstrates that the combination of polycarboxylatedispersant and sulfonated naphthalene-formaldehyde condensate dispersant(S2 and S4) reduces the bleeding of water from cementitious compositionsas compared to using either a polycarboxylate dispersant (S3) orsulfonated naphthalene-formaldehyde condensate dispersant (S1) alone.

[0180] In Table 2 grout mixtures were prepared-that comprised 2100 gm10-20 Silica Sand and 1400 gm Type I/II Portland cement. The flow wasdetermined in accordance with ASTM C 939. TABLE 2 Sample S5 S6 SNF (gm)10.5 10.5 PC (gm) — 2.1 Flow (sec) not measurable due to 15.32segregation Bleed severe slight Segregation severe none

[0181] Table 2 demonstrates the suspending properties of the admixtureformulation. The combination of polycarboxylate dispersant andnaphthalene sulfonate formaldehyde condensate dispersant (S6) decreasedthe bleed and segregation of the grout mixture as compared to use ofnaphthalene sulfonate formaldehyde condensate dispersant alone as shownin Sample 5.

[0182] The mortar mixtures in Table 3 had a water/cement (w/c) ratio of0.35 and comprised 600 gm of 16-35 Silica Sand and 900 gm of Type I/IIPortland cement. The mortar mixtures were prepared with variouspolycarboxylate (PC) dispersants to demonstrate the flow modificationand anti-segregation properties of the invention. The flow wasdetermined in accordance with ASTM C 827 using an ASTM C 230 flow table.Additionally, the maximum measurable flow is 148% and values higher thanthis indicate the material flowed off the table. Segregation wasdetermined visually. TABLE 3 Sample S7 S8 S9 S10 S11 S12 SNF (gm) 4.54.5 — 4.5 4.5 4.5 PC1 (gm) — 1 — — — — PC2 (gm) — — 1 — — — PC3 (gm) — —— 1 — — PC4 (gm) — — — — 1 — PC5 (gm) — — — — — 1 % flow at 0 >148 104116 98.5 90 89 drops segregation yes no no no no no (severe)

[0183] Table 4 demonstrates the flow modification properties of theadmixture formulation with a non-Portland cement binder with mortarmixtures that comprised 600 gm Silica Sand and 400 gm Calcium SulfateHemi-Hydrate. The flow was determined in accordance with ASTM C 827using an ASTM C 230 flow table. TABLE 4 Sample S13 S14 S15 SNF (gm) 1.61.6 PC (gm) — 0.8 % mix water 12 12 12 % flow at 5 drops 51 140 86

[0184] The mortar mixtures of Table 5, comprising 600 gm of 16-36 SilicaSand and 400 gm high alumina cement demonstrated the flow modificationproperties of the admixture formulation with a non-Portland cementbinder. The flow was determined in accordance with ASTM C 827 using anASTM C 230 flow table. TABLE 5 Sample S16 S17 S18 SNF (gm) 4 4 PC (gm) —0.4 % mix water 15 15 15 % flow at 5 drops 108 >148 116 bleed nonesevere none segregation none severe none

[0185] The concrete mixtures of Tables 6-8 were prepared in batches of40 liters using a vertical axis mixer. Aggregates were placed in a mixerfollowed by about 50% of the total mix water and mixed for 1 minute,then cement, admixtures, fiber and the remaining 50% of the total waterand mixed for about 1 minute. The mixing was stopped for 1 minute toallow false set, if present, to take place. Then the mixing wascontinued for another 1 minute.

[0186] To compare the effects of the polycarboxylate/naphthalenedispersants and a thickening agent such as hydroxyethyl cellulose inconcrete, mixtures were measured for initial slump according to ASTM C143, density was measured according to ASTM C 138, bleeding was measuredaccording to ASTM C 232, and the time of initial and final setting weremeasured according to ASTM C 403. Sedimentation tendency was visuallyevaluated in accordance with comparative criteria in 3 categories,namely absent, moderate and strong. Compressive strength was evaluatedin 150 mm steel cubes cast and cured at 20° C. and 95% relativehumidity.

[0187] The concrete mixtures in Table 6 contained the followingcomponents: Portland cement 32.5 II/AL 250 Kg Sand 0-4 mm 950 Kg Crushedgravel 4-12 mm 340 Kg Rounded gravel 20-25 mm 610 Kg SNF 2.5 Kg (1%cement dosage) Air entrainer 0.5 Kg Water 175 Kg (w/c ratio 0.7)

[0188] TABLE 6 Setting Compressive Time strength MPa HEC PC SlumpDensity Bleeding % Sedimentation Minutes 1 7 28 Sample Kg Kg test cmKg/m3 on volume tendency Final Initial day days days S19 — — 25 2320 5moderate 420 570 5 19 27 S20 0.1 — 15 2290 0 absent 549 700 2 12 25 S21— 0.1 25 2325 0 absent 410 570 5 20 27 S22 — 0.2 23 2320 0 absent 420580 5 19 28 S23 — 0.5 11 2315 0 absent 430 590 4 18 27 S24 — 1 5 2315 0absent 430 590 4 18 26

[0189] The fiber-reinforced concrete mixtures in Table 7 contained thefollowing components: cement 52.5 I  315 Kg sand 0-4 mm 1000 Kg peagravel 4-10 mm  820 Kg SNF  10 Kg Alkali Resistant Glass Fiber   8 KgWater  190 Kg (w/c ratio 0.6)

[0190] TABLE 7 Compressive Slump Bleeding Setting Time strength MPa HECPC test Density % on Sedimentation Minutes 1 7 28 Sample Kg Kg cm Kg/m3volume tendency Initial Final day days days S25 — — 23 2340 3 moderate450 580 12 39 54 S26 0.2 — 13 2300 0 absent 530 650  8 32 49 S27 — 0.223 2330 0 absent 440 570 13 40 55 S28 — 0.5 21 2335 0 absent 450 590 1240 55 S29 — 1.5 10 2330 0 absent 460 600 12 39 54

[0191] The self-compacting concrete mixtures in Table 8 contained thefollowing components: Portland cement 42.5 II/AL 320 Kg Fly ash 200 KgSand 0-4 mm 960 Kg Crushed gravel 4-12 mm 280 Kg Rounded gravel 10-16 mm540 Kg SNF  7 Kg (1.35% on binder dosage) Water 190 Kg (w/c ratio 0.59)

[0192] TABLE 8 Compressive Slump Bleeding Setting time strength MPa HECPC flow test Density % on Sedimentation Minutes 1 7 28 Sample Kg Kg cmKg/m3 volume tendency Initial Final day days days S30 — — 62 2420 6strong 480 660 12 32 40 S31 0.2 — 50 2430 0 absent 580 780  7 28 36 S32— 0.2 61 2425 0 absent 470 650 12 31 40 S33 — 0.4 60 2420 0 absent 490670 12 32 41 34S — 1.0 35 2425 0 absent 490 670 11 31 39

[0193] Tables 6-8 demonstrate that the addition of a thickening agentsuch as hydroxyethyl cellulose, polycarboxylate/naphthalene dispersantsstop the bleeding of the concrete mixtures. However, in contrast to themixtures containing polycarboxylate/naphthalene dispersants, those thatcontained hydroxyethyl cellulose had reduced workability and compressivestrength with increased setting time. The mixtures containing thepolycarboxylate/naphthalene dispersants did not have any of the adverseeffects of the mixture containing hydroxyethyl cellulose.

[0194] It should be appreciated that there is no limitation to thespecific embodiments described above, but includes variations,modifications and equivalent embodiments defined by the followingclaims. The embodiments disclosed are not necessarily in thealternative, as various embodiments of the invention may be combined toprovide desired characteristics or results.

What is claimed is:
 1. An admixture formulation for cementitiouscompositions comprising at least one polycarboxylate dispersant and atleast one naphthalene dispersant, wherein the amount of polycarboxylatedispersant is about 1% to about 99% and the amount of naphthalenedispersant is about 1% to about 99% based on the total dry weight of theadmixture formulation.
 2. The composition of claim 1 wherein theadmixture formulation comprises about 5% to about 95% polycarboxylatedispersant and about 5% to about 95% naphthalene dispersant based on thetotal dry weight of the admixture formulation.
 3. The composition ofclaim 2 wherein the admixture formulation comprises about 10% to about90% polycarboxylate dispersant and about 10% to about 90% naphthalenedispersant based on the total dry weight of the admixture formulation.4. The composition of claim 1 further comprising at least one of setaccelerators, set retarders, air-entraining or air detraining agents,corrosion inhibitors, pigments, wetting agents, water soluble polymers,rheology modifying agents, water repellents, fibers, dampproofingadmixtures, gas formers, permeability reducers, pumping aids, fungicidaladmixtures, germicidal admixtures, insecticidal admixtures, finelydivided mineral admixtures, alkali-reactivity reducer, bondingadmixtures, strength enhancing agents, shrinkage reducing agents, andmixtures thereof.
 5. A cementitious composition comprising hydrauliccement, at least one polycarboxylate dispersant and at least onenaphthalene dispersant, wherein the amount of polycarboxylate dispersantprimary active ingredient is about 0.001% to about 10% and the amount ofnaphthalene dispersant primary active ingredient is about 0.001% toabout 10% primary active ingredient based on the total dry weight ofcementitious material.
 6. The composition of claim 5 wherein the amountof polycarboxylate dispersant is about 0.01% to about 5% and the amountof naphthalene dispersant is about 0.01% to about 5% based on the totaldry weight of cementitious material.
 7. The composition of claim 6wherein the amount of polycarboxylate dispersant is about 0.1% to about2% and the amount of naphthalene dispersant is about 0.1% to about 2%based on the total dry weight of cementitious material.
 8. Thecomposition of claim 5, wherein the hydraulic cement is selected fromthe group consisting of portland cement, masonry cement, high aluminacement, refractory cement, magnesia cement, calcium sulfate hemi-hydratecement, calcium sulfoaluminate cement, and mixtures thereof.
 9. Thecomposition of claim 1 or 5 wherein the naphthalene dispersant is atleast one of naphthalene sulfonate formaldehyde condensate, betanaphthalene sulfonates, or sodium naphthalene sulfate formaldehydecondensate resins.
 10. The composition of claim 1 or 5 wherein thecomposition further comprises an unaffected non-polycarboxylatedispersant from the group consisting of at least one of melamineformaldehyde condensate resins, salts of melamine formaldehydecondensate resins, carboxylic acids, salts of carboxylic acids, calciumlignosulfonates, and mixtures thereof.
 11. The composition of claim 1 or5 wherein the composition further comprises at least one oligomericdispersant, wherein the oligomeric dispersant is a reaction product ofcomponent A, optionally component B, and component C; wherein eachcomponent A is independently a nonpolymeric, multi-functional moiety orcombination of mono or multifunctional moieties that adsorbs onto acementitious particle, and contains at least one residue derived from afirst component selected from the group consisting of phosphates,phosphonates, phosphinates, hypophosphites, sulfates, sulfonates,sulfinates, alkyl trialkoxy silanes, alkyl triacyloxy silanes, alkyltriaryloxy silanes, borates, boronates, boroxines, phosphoramides,amines, amides, quaternary ammonium groups, carboxylic acids, carboxylicacid esters, alcohols, carbohydrates, phosphate esters of sugars, borateesters of sugars, sulfate esters of sugars, salts of any of thepreceding moieties, and mixtures thereof; wherein component B is anoptional moiety, where if present, each component B is independently anonpolymeric moiety that is disposed between the component A moiety andthe component C moiety, and is derived from a second component selectedfrom the group consisting of linear saturated hydrocarbons, linearunsaturated hydrocarbons, saturated branched hydrocarbons, unsaturatedbranched hydrocarbons, alicyclic hydrocarbons, heterocyclichydrocarbons, aryl, phosphoester, nitrogen containing compounds, andmixtures thereof; and wherein component C is at least one moiety that isa linear or branched water soluble, nonionic polymer substantiallynon-adsorbing to cement particles, and is selected from the groupconsisting of poly(oxyalkylene glycol), poly(oxyalkylene amine),poly(oxyalkylene diamine), monoalkoxy poly(oxyalkylene amine),monoaryloxy poly(oxyalkylene amine), monoalkoxy poly(oxyalkyleneglycol), monoaryloxy poly(oxyalkylene glycol), poly(vinyl pyrrolidones),poly(methyl vinyl ethers), poly(ethylene imines), poly(acrylamides),polyoxazoles, and mixtures thereof.
 12. The composition of claim 1 or 5wherein the polycarboxylate dispersant for cementitious compositions isat least one polycarboxylate high range water reducing dispersantselected from the group consisting of: a) a dispersant of Formula (I):

wherein in Formula (I) X is at least one of hydrogen, an alkali earthmetal ion, an alkaline earth metal ion, ammonium ion, or amine; R is atleast one of C₁ to C₆ alkyl(ene) ether or mixtures thereof or C₁ to C₆alkyl(ene) imine or mixtures thereof; Q is at least one of oxygen, NH,or sulfur; p is a number from 1 to about 300 resulting in at least oneof a linear side chain or branched side chain; R₁ is at least one ofhydrogen, C₁ to C₂₀ hydrocarbon, or functionalized hydrocarboncontaining at least one of —OH, —COOH, an ester or amide derivative of—COOH, sulfonic acid, an ester or amide derivative of sulfonic acid,amine, or epoxy; Y is at least one of hydrogen, an alkali earth metalion, an alkaline earth metal ion, ammonium ion, amine, a hydrophobichydrocarbon or polyalkylene oxide moiety that functions as a defoamer;m, m′, m″, n, n′, and n″ are each independently 0 or an integer between1 and about 20; Z is a moiety containing at least one of i) at least oneamine and one acid group, ii) two functional groups capable ofincorporating into the backbone selected from the group consisting ofdianhydrides, dialdehydes, and di-acid-chlorides, or iii) an imideresidue; and wherein a, b, c, and d reflect the mole fraction of eachunit wherein the sum of a, b, c, and d equal one, wherein a, b, c, and dare each a value greater than or equal to zero and less than one, and atleast two of a, b, c, and d are greater than zero; b) a dispersant ofFormula (II):

wherein in Formula (II): A is COOM or optionally in the “y” structure anacid anhydride group (—CO—O—CO—) is formed in place of the A groupsbetween the carbon atoms to which the A groups are bonded to form ananhydride; B is COOM; M is hydrogen, a transition metal cation, theresidue of a hydrophobic polyalkylene glycol or polysiloxane, an alkalimetal ion, an alkaline earth metal ion, ferrous ion, aluminum ion,(alkanol)ammonium ion, or (alkyl)ammonium ion; R is a C₂₋₆ alkyleneradical; RI is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group; x, y,and z are a number from 0.01 to 100; m is a number from 1 to 100; and nis a number from 10 to 100; c) a dispersant comprising at least onepolymer or a salt thereof having the form of a copolymer of i) a maleicanhydride half-ester with a compound of the formula RO(AO)_(m)H, whereinR is a C₁-C₂₀ alkyl group, A is a C₂₋₄ alkylene group, and m is aninteger from 2-16; and ii) a monomer having the formulaCH₂═CHCH₂—(OA)_(n)OR, wherein n is an integer from 1-90 and R is a C₁₋₂₀alkyl group; d) a dispersant obtained by copolymerizing 5 to 98% byweight of an (alkoxy)polyalkylene glycol mono(meth)acrylic ester monomer(a) represented by the following general formula (1):

wherein R₁ stands for hydrogen atom or a methyl group, R₂O for onespecies or a mixture of two or more species of oxyalkylene group of 2 to4 carbon atoms, providing two or more species of the mixture may beadded either in the form of a block or in a random form, R₃ for ahydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m is a valueindicating the average addition mol number of oxyalkylene groups that isan integer in the range of 1 to 100, 95 to 2% by weight of a(meth)acrylic acid monomer (b) represented by the above general formula(2), wherein R₄ and R₅ are each independently a hydrogen atom or amethyl group, and M₁ for a hydrogen atom, a monovalent metal atom, adivalent metal atom, an ammonium group, or an organic amine group, and 0to 50% by weight of other monomer (c) copolymerizable with thesemonomers, provided that the total amount of (a), (b), and (c) is 100% byweight; e) a graft polymer that is a polycarboxylic acid or a saltthereof, having side chains derived from at least one species selectedfrom the group consisting of oligoalkyleneglycols, polyalcohols,polyoxyalkylene amines, and polyalkylene glycols; f) a dispersant ofFormula (III):

wherein in Formula (III): D=a component selected from the groupconsisting of the structure d1, the structure d2, and mixtures thereof;X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl;Y=H or —COOM; R=H or CH₃; Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ wheren=2 to 6, —COOR₃, or —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃, —CONHC(CH₃)₂CH₂SO₃M, —COO(CHR₄)_(n)OH where n=2 to 6, or —O(CH₂)_(n)OR₄ wherein n=2to 6; R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄ randomcopolymer of oxyethylene units and oxypropylene units where m=10 to 500and wherein the amount of oxyethylene in the random copolymer is fromabout 60% to 100% and the amount of oxypropylene in the random copolymeris from 0% to about 40%; R₄=H, Methyl, C₂ to about C₆ Alkyl, or about C₆to about C₁₀ aryl; M=H, Alkali Metal, Alkaline Earth Metal, Ammonium,Amine, triethanol amine, Methyl, or C₂ to about C₆ Alkyl; a=0 to about0.8; b=about 0.2 to about 1.0; c=0 to about 0.5; d=0 to about 0.5; andwherein a, b, c, and d represent the mole fraction of each unit and thesum of a, b, c, and d is 1.0; g) a dispersant of Formula (IV):

wherein in Formula (IV): the “b” structure is one of a carboxylic acidmonomer, an ethylenically unsaturated monomer, or maleic anhydridewherein an acid anhydride group (—CO—O—CO—) is formed in place of thegroups Y and Z between the-carbon atoms to which the groups Y and Z arebonded respectively, and the “b” structure must include at least onemoiety with a pendant ester linkage and at least one moiety with apendant amide linkage; X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-MethylPhenyl, p-Ethyl Phenyl, Carboxylated Phenyl, or Sulfonated Phenyl; Y=H,—COOM, —COOH, or W; W=a hydrophobic defoamer represented by the formulaR₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s, t, and u areintegers from 0 to 200 with the proviso that t>(s+u) and wherein thetotal amount of hydrophobic defoamer is present in an amount less thanabout 10% by weight of the polycarboxylate dispersant; Z=H, —COOM,—O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, —(CH₂)_(n)OR₃ where n=0 to 6, or—CONHR₃; R₁=H, or CH₃; R₂, R₃, are each independently a random copolymerof oxyethylene units and oxypropylene units of the general formula—(CH(R₁)CH₂O)_(m)R₄ where m=10 to 500 and wherein the amount ofoxyethylene in the random copolymer is from about 60% to 100% and theamount of oxypropylene in the random copolymer is from 0% to about 40%;R₄=H, Methyl, or C₂ to C₈ Alkyl; R₅=C₁ to C ₈ alkyl or C₆ to C₁₈ alkylaryl; M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine, monoethanolamine, diethanol amine, triethanol amine, morpholine, imidazole;a=0.01-0.8; b=0.2-0.99; C 0-0.5; and wherein a, b, c represent the molefraction of each unit and the sum of a, b, and c, is 1; h) a randomcopolymer corresponding to the following Formula (V) in free acid orsalt form having the following monomer units and numbers of monomerunits:

wherein A is selected from the moieties (i) or (ii) (i) —CR₁R₂—CR₃R₄—

wherein R₁ and R₃ are selected from substituted benzene, C₁₋₈ alkyl,C₂₋₈ alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy, carboxyl, hydrogen, and aring, R₂ and R₄ are selected from the group consisting of hydrogen andC₁₋₄ alkyl, wherein R₁ and R₃ can together with R₂ and/or R₄ when R₂and/or R₄ are C₁₋₄ alkyl form the ring; R₇, R₈, R₉, and R₁₀ areindividually selected from the group consisting of hydrogen, C₁₋₆ alkyl,and a C₂₋₈ hydrocarbon chain, wherein R₁ and R₃ together with R₇ and/orR₈, R₉, and R₁₀ form the C₂₋₈ hydrocarbon chain joining the carbon atomsto which they are attached, the hydrocarbon chain optionally having atleast one anionic group, wherein the at least one anionic group isoptionally sulfonic; M is selected from the group consisting ofhydrogen, and the residue of a hydrophobic polyalkylene glycol or apolysiloxane, with the proviso that when A is (ii) and M is the residueof a hydrophobic polyalkylene glycol, M must be different from the group—(R₅O)_(m)R₆; R₅ is a C₂₋₈ alkylene radical; R₆ is selected from thegroup consisting of C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl and phenyl; n, x, and zare numbers from 1 to 100; y is 0 to 100; m is 2 to 1000; the ratio of xto (y+z) is from 1:10 to 10:1 and the ratio of y:z is from 5:1 to 1:100;i) a copolymer of oxyalkyleneglycol-alkenyl ethers and unsaturateddicarboxylic acids, comprising: i) 0 to 90 mol % of at least onecomponent of the formula 3a or 3b:

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100, —NHR₂, —N(R²)₂ or mixtures thereof in which R²═R¹ or —CO—NH₂; andwherein Y is an oxygen atom or —NR²; ii) 1 to 89 mol % of components ofthe general formula 4:

wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon radicalcontaining from 1 to 5 carbon atoms, p is 0 to 3, and R₁ is hydrogen, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonic substituted arylradical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,and iii) 0.1 to 10 mol % of at least one component of the formula 5a or5b:

wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is —COOR₅, —W—R₇,—CO—[—NH—(CH2)3)—]_(s)—W—R₇, —CO—O—(CH₂)_(z)—W—R₇, a radical of thegeneral formula:

or —(CH₂)_(z)—V—(CH₂)_(z)—CH═CH—R₁, or when S is —COOR₅ or —COOM_(a), U₁is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O— or —OCH₂, V is—O—CO—C₆H₄—CO—O— or —W—, and W is

R4 is a hydrogen atom or a methyl radical, R5 is an aliphatichydrocarbon radical containing 3 to 20 carbon atoms, a cycloaliphatichydrocarbon radical containing 5 to 8 carbon atoms or an aryl radicalcontaining 6 to 14 carbon atoms, R₆═R₁ or

R₇═R₁ or

r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and z is 0 to 4;iv) 0 to 90 mol % of at least one component of the formula 6a, 6b, or6c:

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100, —NH—(C_(m)H_(2m)O)_(n)—R¹, —NHR₂, —N(R²)₂ or mixtures thereof inwhich R²═R¹ or —CO—NH₂; and wherein Y is an oxygen atom or —NR²; j) acopolymer of dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, comprising: i) 1 to 90 mol. % of at least onemember selected from the group consisting of structural units of Formula7a and Formula 7b:

wherein M is H, a monovalent metal cation, a divalent metal cation, anammonium ion or an organic amine; a is ½ when M is a divalent metalcation or 1 when M is a monovalent metal cation; wherein R¹ is —OM_(a),or —O—(C_(m)H_(2m)O)_(n)—R² wherein R² is H, a C₁₋₂₀ aliphatichydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); m is 2 to 4; nis 1 to 200; ii) 0.5 to 80 mol. % of the structural units of Formula 8:

wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon; p is 0 to 3; R² is H, aC₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or aC₆₋₁₄ aryl that is optionally substituted with at least one memberselected from the group consisting of —COOM_(a), —(SO₃)M_(a), and—(PO₃)M_(a2); m is 2 to 4; n is 1 to 200; iii) 0.5 to 80 mol. %structural units selected from the group consisting of Formula 9a andFormula 9b:

wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is optionallysubstituted with at least one hydroxyl group, —(C_(m)H_(2m)O)_(n)—R²,—CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); M is H, amonovalent metal cation, a divalent metal cation, an ammonium ion or anorganic amine; a is {fraction (1/2)} when M is a divalent metal cationor 1 when M is a monovalent metal cation; R² is H, a C₁₋₂₀ aliphatichydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); m is 2 to 4; nis 1 to 200; iv) 1 to 90 mol. % of structural units of Formula 10

wherein R⁵ is methyl, or methylene group, wherein R⁵ forms one or more 5to 8 membered rings with R⁷; R⁶ is H, methyl, or ethyl; R⁷ is H, a C₁₋₂₀aliphatic hydrocarbon, a C₆₋₁₄ aryl that is optionally substituted withat least one member selected from the group consisting of —COOM_(a),—(SO₃)M_(a), and —(PO₃)M_(a2), a C₅₋₈ cycloaliphatic hydrocarbon,—OCOR⁴, —OR⁴, or —COOR⁴, wherein R⁴ is H, a C₁₋₂₀ aliphatic hydrocarbonthat is optionally substituted with at least one —OH,—(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or aC6-14 aryl residue that is optionally substituted with a member selectedfrom the group consisting of —COOM_(a), —(SO₃)M_(a), —(PO₃)M_(a2). 13.The composition of claim 5 further comprising a cement admixture oradditive that is selected from the group consisting of set accelerators,set retarders, air-entraining or air detraining agents, corrosioninhibitors, pigments, wetting agents, water soluble polymers, rheologymodifying agents, water repellents, fibers, dampproofing admixtures, gasformers, permeability reducers, pumping aids, fungicidal admixtures,germicidal admixtures, insecticidal admixtures, finely divided mineraladmixtures, alkali-reactivity reducer, bonding admixtures, strengthenhancing agents, shrinkage reducing agents, aggregates, pozzolans andmixtures thereof.
 14. The composition of claim 13, wherein the setaccelerator comprises at least one of: a) a nitrate salt of an alkalimetal, alkaline earth metal, or aluminum; b) a nitrite salt of an alkalimetal, alkaline earth metal, or aluminum; c) a thiocyanate of an alkalimetal, alkaline earth metal or aluminum; d) an alkanolamine; e) athiosulphate of an alkali metal, alkaline earth metal, or aluminum; f) ahydroxide of an alkali metal, alkaline earth metal, or aluminum; g) acarboxylic acid salt of an alkali metal, alkaline earth metal, oraluminum; h) a polyhydroxylalkylamine; or i) a halide salt of an alkalimetal or alkaline earth metal.
 15. The composition of claim 13 whereinthe set retarder is selected from the group consisting of an oxy-boroncompound, lignin, a polyphosphonic acid, a carboxylic acid, ahydroxycarboxylic acid, polycarboxylic acid, hydroxylated carboxylicacid, fumaric, itaconic, malonic, borax, gluconic, and tartaric acid,lignosulfonates, ascorbic acid, isoascorbic acid, sulphonic acid-acrylicacid copolymer, and their corresponding salts, polyhydroxysilane,polyacrylamide, carbohydrates and mixtures thereof.
 16. The compositionof claim 13, wherein the aggregate is at least one of silica, quartz,crushed round marble, glass spheres, granite, limestone, calcite,feldspar, alluvial sands, heavy weight aggregate, light weightaggregate, metallic particles, and sand.
 17. The composition of claim13, wherein the pozzolan is at least one of natural pozzolan, fly ash,silica fume, calcined clay, and blast furnace slag.
 18. A method ofmaking a cementitious composition comprising mixing the composition ofclaim 5 containing cementitibus material with water.
 19. The method ofclaim 18 wherein the amount of polycarboxylate dispersant is about 0.01%to about 5% and the amount of naphthalene dispersant is about 0.01% toabout 5% based on the total dry weight of cementitious material.
 20. Themethod of claim 18 wherein the amount of polycarboxylate dispersant isabout 0.1% to about 2% and the amount of naphthalene dispersant is about0.1% to about 2% based on the dry weight of cementitious material. 21.The method of claim 18, wherein the hydraulic cement is selected fromthe group consisting of portland cement, masonry cement, alumina cement,refractory cement, magnesia cement, calcium sulfate hemi-hydrate cement,calcium sulfoaluminate cement, and mixtures thereof.
 22. The method ofclaim 18 further comprising adding a cement admixture or additive to thecementitious composition that is selected from the group consisting ofset accelerators, set retarders, air-entraining or air detrainingagents, corrosion inhibitors, pigments, wetting agents, water solublepolymers, rheology modifying agents, water repellents, fibers,dampproofing admixtures, gas formers, permeability reducers, pumpingaids, fungicidal admixtures, germicidal admixtures, insecticidaladmixtures, finely divided mineral admixtures, alkali-reactivityreducer, bonding admixtures, strength enhancing agents, shrinkagereducing agents, aggregates, pozzolans and mixtures thereof.
 23. Themethod of claim 22, wherein the set accelerator comprises at least oneof: a) a nitrate salt of an alkali metal, alkaline earth metal, oraluminum; b) a nitrite salt of an alkali metal, alkaline earth metal, oraluminum; c) a thiocyanate of an alkali metal, alkaline earth metal oraluminum; d) an alkanolamine; e) a thiosulphate of an alkali metal,alkaline earth metal, or aluminum; f) a hydroxide of an alkali metal,alkaline earth metal, or aluminum; g) a carboxylic acid salt of analkali metal, alkaline earth metal, or aluminum; h) apolyhydroxylalkylamine; or i) a halide salt of an alkali metal oralkaline earth metal.
 24. The method of claim 22 wherein the setretarder is selected from the group consisting of an oxy-boron compound,lignin, a polyphosphonic acid, a carboxylic acid, a hydroxycarboxylicacid, polycarboxylic acid, hydroxylated carboxylic acid, fumaric,itaconic, malonic, borax, gluconic, and tartaric acid, lignosulfonates,ascorbic acid, isoascorbic acid, sulphonic acid-acrylic acid copolymer,and their corresponding salts, polyhydroxysilane, polyacrylamide,carbohydrates and mixtures thereof.
 25. The method of claim 22, whereinthe aggregate is at least one of silica, quartz, crushed round marble,glass spheres, granite, limestone, calcite, feldspar, alluvial sands,heavy weight aggregate, light weight aggregate, metallic particles, andsand.
 26. The method of claim 22, wherein the pozzolan is at least oneof natural pozzolan, fly ash, silica fume, calcined clay, and blastfurnace slag.
 27. The method of claim 18 wherein the naphthalenedispersant is at least one of naphthalene sulfonate formaldehydecondensate, beta naphthalene sulfonates, or sodium naphthalene sulfateformaldehyde condensate resins.
 28. The method of claim 18 wherein thecomposition further comprises an unaffected non-polycarboxylatedispersant from the group consisting of at least one of melamineformaldehyde condensate resins, salts of melamine formaldehydecondensate resins, carboxylic acids, salts of carboxylic acids, calciumlignosulfonates, and mixtures thereof.
 29. The method of claim 18wherein the composition further comprises at least one oligomericdispersant, wherein the oligomeric dispersant is a reaction product ofcomponent A, optionally component B, and component C; wherein eachcomponent A is independently a nonpolymeric, multi-functional moiety orcombination of mono or multifunctional moieties that adsorbs onto acementitious particle, and contains at least one residue derived from afirst component selected from the group consisting of phosphates,phosphonates, phosphinates, hypophosphites, sulfates, sulfonates,sulfinates, alkyl trialkoxy silanes, alkyl triacyloxy silanes, alkyltriaryloxy silanes, borates, boronates, boroxines, phosphoramides,amines, amides, quaternary ammonium groups, carboxylic acids, carboxylicacid esters, alcohols, carbohydrates, phosphate esters of sugars, borateesters of sugars, sulfate esters of sugars, salts of any of thepreceding moieties, and mixtures thereof; wherein component B is anoptional moiety, where if present, each component B is independently anonpolymeric moiety that is disposed between the component A moiety andthe component C moiety, and is derived from a second component selectedfrom the group consisting of linear saturated hydrocarbons, linearunsaturated hydrocarbons, saturated branched hydrocarbons, unsaturatedbranched hydrocarbons, alicyclic hydrocarbons, heterocyclichydrocarbons, aryl, phosphoester, nitrogen containing compounds, andmixtures thereof; and wherein component C is at least one moiety that isa linear or branched water soluble, nonionic polymer substantiallynon-adsorbing to cement particles, and is selected from the groupconsisting of poly(oxyalkylene glycol), poly(oxyalkylene amine),poly(oxyalkylene diamine), monoalkoxy poly(oxyalkylene amine),monoaryloxy poly(oxyalkylene amine), monoalkoxy poly(oxyalkyleneglycol), monoaryloxy poly(oxyalkylene glycol), poly(vinyl pyrrolidones),poly(methyl vinyl ethers), poly(ethylene imines), poly(acrylamides),polyoxazoles, and mixtures thereof.
 30. A method of making acementitious composition comprising mixing the composition of claim 12containing cementitious material with water.
 31. The method of claim 30wherein the amount of polycarboxylate dispersant is about 0.01% to about5% and the amount of naphthalene dispersant is about 0.01% to about 5%based on the total dry weight of cementitious material.
 32. The methodof claim 30 wherein the amount of polycarboxylate dispersant is about0.1% to about 2% and the amount of naphthalene dispersant is about 0.1%to about 2% based on the dry weight of cementitious material.
 33. Themethod of claim 30, wherein the hydraulic cement is selected from thegroup consisting of portland cement, masonry cement, alumina cement,refractory cement, magnesia cement, calcium sulfate hemi-hydrate cement,calcium sulfoaluminate cement, and mixtures thereof.
 34. The method ofclaim 30 further comprising adding a cement admixture or additive to thecementitious composition that is selected from the group consisting ofset accelerators, set retarders, air-entraining or air detrainingagents, corrosion inhibitors, pigments, wetting agents, water solublepolymers, rheology modifying agents, water repellents, fibers,dampproofing admixtures, gas formers, permeability reducers, pumpingaids, fungicidal admixtures, germicidal admixtures, insecticidaladmixtures, finely divided mineral admixtures, alkali-reactivityreducer, bonding admixtures, strength enhancing agents, shrinkagereducing agents, aggregates, pozzolans and mixtures thereof.
 35. Themethod of claim 34, wherein the set accelerator comprises at least oneof: a) a nitrate salt of an alkali metal, alkaline earth metal, oraluminum; b) a nitrite salt of an alkali metal, alkaline earth metal, oraluminum; c) a thiocyanate of an alkali metal, alkaline earth metal oraluminum; d) an alkanolamine; e) a thiosulphate of an alkali metal,alkaline earth metal, or aluminum; f) a hydroxide of an alkali metal,alkaline earth metal, or aluminum; g) a carboxylic acid salt of analkali metal, alkaline earth metal, or aluminum; h) apolyhydroxylalkylamine; or i) a halide salt of an alkali metal oralkaline earth metal.
 36. The method of claim 34 wherein the setretarder is selected from the group consisting of an oxy-boron compound,lignin, a polyphosphonic acid, a carboxylic acid, a hydroxycarboxylicacid, polycarboxylic acid, hydroxylated carboxylic acid, fumaric,itaconic, malonic, borax, gluconic, and tartaric acid, lignosulfonates,ascorbic acid, isoascorbic acid, sulphonic acid-acrylic acid copolymer,and their corresponding salts, polyhydroxysilane, polyacrylamide,carbohydrates and mixtures thereof.
 37. The method of claim 34, whereinthe aggregate is at least one of silica, quartz, crushed round marble,glass spheres, granite, limestone, calcite, feldspar, alluvial sands,and sand.
 38. The method of claim 34, wherein the pozzolan is at leastone of natural pozzolan, fly ash, silica fume, calcined clay, and blastfurnace slag.
 39. The method of claim 30 wherein the naphthalenedispersant is at least one of naphthalene sulfonate formaldehydecondensate, beta naphthalene sulfonates, or sodium naphthalene sulfateformaldehyde condensate resins.
 40. The method of claim 30 wherein thecomposition further comprises an unaffected non-polycarboxylatedispersant from the group consisting of at least one of melamineformaldehyde condensate resins, salts of melamine formaldehydecondensate resins, carboxylic acids, salts of carboxylic acids, calciumlignosulfonates, and mixtures thereof.
 41. The method of claim 30wherein the composition further comprises at least one oligomericdispersant, wherein the oligomeric dispersant is a reaction product ofcomponent A, optionally component B, and component C; wherein eachcomponent A is independently a nonpolymeric, multi-functional moiety orcombination of mono or multifunctional moieties that adsorbs onto acementitious particle, and contains at least one residue derived from afirst component selected from the group consisting of phosphates,phosphonates, phosphinates, hypophosphites, sulfates, sulfonates,sulfinates, alkyl trialkoxy silanes, alkyl triacyloxy silanes, alkyltriaryloxy silanes, borates, boronates, boroxines, phosphoramides,amines, amides, quaternary ammonium groups, carboxylic acids, carboxylicacid esters, alcohols, carbohydrates, phosphate esters of sugars, borateesters of sugars, sulfate esters of sugars, salts of any of thepreceding moieties, and mixtures thereof; wherein component B is anoptional moiety, where if present, each component B is independently anonpolymeric moiety that is disposed between the component A moiety andthe component C moiety, and is derived from a second component selectedfrom the group consisting of linear saturated hydrocarbons, linearunsaturated hydrocarbons, saturated branched hydrocarbons, unsaturatedbranched hydrocarbons, alicyclic hydrocarbons, heterocyclichydrocarbons, aryl, phosphoester, nitrogen containing compounds, andmixtures thereof; and wherein component C is at least one moiety that isa linear or branched water soluble, nonionic polymer substantiallynon-adsorbing to cement particles, and is selected from the groupconsisting of poly(oxyalkylene glycol), poly(oxyalkylene amine),poly(oxyalkylene diamine), monoalkoxy poly(oxyalkylene amine),monoaryloxy poly(oxyalkylene amine), monoalkoxy poly(oxyalkyleneglycol), monoaryloxy poly(oxyalkylene glycol), poly(vinyl pyrrolidones),poly(methyl vinyl ethers), poly(ethylene imines), poly(acrylamides),polyoxazoles, and mixtures thereof.